CN105176370B - A kind of protective film and its manufacturing method for being bonded arc side - Google Patents
A kind of protective film and its manufacturing method for being bonded arc side Download PDFInfo
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- CN105176370B CN105176370B CN201510447066.XA CN201510447066A CN105176370B CN 105176370 B CN105176370 B CN 105176370B CN 201510447066 A CN201510447066 A CN 201510447066A CN 105176370 B CN105176370 B CN 105176370B
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Abstract
The invention discloses a kind of protective films and its manufacturing method for being bonded arc side, screen protecting film are made using organic siliconresin synthesis and base material selection, which will not play side when being bonded curved edge screen.The protective film of the present invention; include PET base material; PET base material does cure process and obtains cure process layer on one side; PET base material another side does coating silica gel and handles to obtain coating silica gel layer; the attached last layer PET stripping films of one side of the coating silica gel layer away from PET base material, the attached last layer PET cuticular layers of one side of the cure process layer away from PET base material.The present invention provides a kind of protective film for being bonded arc side, arc side 2.0~3.0mm of radius, which is bonded with the perfection of curved edge screen.
Description
Technical field
The present invention relates to a kind of protective films, are selected more particularly, to a kind of synthesis of organic siliconresin with base material, using gluing
The protective film for being bonded arc side prepared by material technology.
Background technology
Mobile phone screen has the advantages that low energy consumption, light-weight, radiationless, flicker free, is the display of mainstream on the market at present
Screen.As electronics industry develops, for the more preferable visual experience of screen, edge and screen glass are all designed for many smart mobile phones
Camber.In order to adapt to this curved edge, the screen protecting film occurred currently on the market is mainly PET material protective films.But
It is that PET materials itself are harder, can plays side when being bonded curved edge screen, can not be bonded entirely with curved edge screen.So that
The electronic product for having arc side currently on the market can only be partly bonded, and touch screen is caused to knock hand, influences visual effect.
The content of the invention
The purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of protective film and its system for being bonded arc side
Method is made, screen protecting film is made using organic siliconresin synthesis and base material selection, when which is bonded curved edge screen
Time will not play side, and be bonded with the perfection of curved edge screen.
In order to achieve the above objectives, the present invention uses following scheme：
A kind of protective film for being bonded arc side, includes PET base material, and PET base material is done cure process and obtained at hardening on one side
Layer is managed, PET base material another side does coating silica gel and handles to obtain coating silica gel layer, and coating silica gel layer (the inside at coating silica gel) is separate
The attached last layer PET stripping films of one side of PET base material, cure process layer (cure process face) enclose one on one side away from PET base material
Layer PET cuticular layers.
Further, in wherein some embodiments, the PET cuticular layers do and obtain silica gel treatment layer after silica gel treatment,
One side of the silica gel treatment layer away from PET cuticular layers is bonded with cure process layer (cure process face) and PET cuticular layers are done at silica gel
It is bonded again with the inside at hardening after reason.
Further, in wherein some embodiments, the hardened layer of the cure process layer is mainly applied using radiation-curable
Material, the raw material composition and parts by weight of the radiation-curable coating are：
Polyurethane acroleic acid prepolymer resin is using Shanghai Ke Li printing materials Co., Ltd；
Acrylic monomers is：Acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate a kind of extremely combination (on
Hai Kaiyin Chemical Co., Ltd.s)；
Photoinitiator is：Thioxanthones (triaryl salt compounded of iodine, triaryl salt) is used in mixed way photoinitiator；
Auxiliary agent is：Cellulose nitrate film forming agent, ethyl cellulose；
Solvent is：One kind of esters, ketone or benzene kind solvent and combinations thereof.
Further, in wherein some embodiments, the coating silica gel layer, silica gel treatment layer are synthesized using organosiloxane
Coating, the raw material composition and parts by weight of organosiloxane synthetic paint are：
Hydroxyl polysiloxane is selected：Trimethyl triethoxysilane, diethylamino phenyl oxosilane, three ethoxy silane of aminomethyl phenyl
One kind and combinations thereof；
Epoxy resin is selected：Phenol type novolac epoxy resin, one kind of o-cresol type novolac epoxy resin and combinations thereof；
Coupling agent is selected：Positive silicic acid second is cruel, one kind of poly- phthalein amine and combinations thereof；
Curing agent is selected：Dibutyl tin laurate, one kind of m-phenylene diamine (MPD) and combinations thereof；
Catalyst：Platinum curing agent；
Solvent：Toluene, dimethylbenzene, one kind and combinations thereof of ethyl acetate.
A kind of manufacturing method for the protective film for being bonded arc side, manufacturing method are as follows：
(1), thickness is selected as the higher PET base material of 20~50 μm of flexibilities, after PET base material is done on one side inside at hardening
Cure process layer, the hardened layer of cure process layer is mainly using radiation-curable coating, and hardening face thickness is 3~4 μm, coating
Using intaglio plate coating, film layer does 1~5u of thickness, and ultraviolet light cures；
(2), the attached last layer PET cuticular layers outside cure process layer；
(3), do the high silica gel treatment of flexibility in PET base material another side and obtain coating silica gel layer, 20 μm of thickness；
Silica gel preparation method：Proportioned hydroxyl polysiloxane (linear polysiloxanes) and solvent are added in agitating and heating to return
Flow 4~6h (hour)；Then add with epoxy resin high-volume, return stirring 2h (hour)；Then solvent under reduced pressure is steamed again
Go out to solid content 74~86%, then be warming up to 80~100 DEG C, add in coupling agent, back flow reaction 2h (hour), you can obtain organic
Silicones stands 5h (hour), adds in curing agent and catalyst stirring 1h (hour)；
(4), attached last layer PET stripping films outside coating silica gel layer.
Further, in wherein some embodiments, in the step (2), PET cuticular layer internal layers obtain after doing silica gel treatment
Silica gel treatment layer, silica gel treatment layer are bonded again with cure process layer 11 (cure process face).
The present invention provides a kind of protective film for being bonded arc side, arc side 2.0~3.0mm of radius, protective film fitting arc
Side will not be played when edge screen, and is bonded with the perfection of curved edge screen.
Description of the drawings
Fig. 1 is the structure diagram of the embodiment of the present invention.
Reference sign：
PET base material 10, cure process layer 11, coating silica gel layer 12, PET cuticular layers 20, silica gel treatment layer 21, PET are removed
Film 30.
Specific embodiment
For that can further appreciate that the feature of the present invention, technological means and the specific purposes reached, function, this hair is parsed
The advantages of bright and spirit, by the present invention is further elaborated by the following examples.
Generally conventional three-layer protection film is made of PET stripping films 30 (PET release films), PET base material 10 and PET cuticular layers 20
's.
PET base material 10 does cure process and obtains cure process layer 11 on one side, and another side does coating silica gel and handles to obtain silica gel
Coating layer 12.Coating silica gel layer 12 (the inside at coating silica gel) attached last layer PET stripping films 30, cure process layer 11 is (at hardening
Reason face) attached last layer PET cuticular layers 20.PET cuticular layers 20 do the silica gel treatment layer 21 after silica gel treatment and cure process layer 11
(cure process face) is bonded.
Thickness is selected to be done on one side inside at hardening in PET base material 10 for the higher PET base material 10 of 20~50 μm of flexibilities
Cure process layer 11 afterwards, and attached last layer PET cuticular layers 20；The high coating silica gel of flexibility is done in 10 another side of PET base material
Layer 12, then attached last layer PET stripping films 30.
The higher PET base material 10 of flexibility, for flexibility bioassay standard with the cylinder mandrel rod of a diameter of 80mm, body length is big
In 25mm.2 ± 0.5mm of radius of curvature.Cylinder mandrel rod is marked into and 3 graduation marks at 0 point clockwise.Base material is selected as length
The PET base material 10 of 150mm wide 30mm.
Test temperature is 40~75 DEG C, is measured in the range of humidity point 40~75%.
First that cylindrical side is horizontal positioned, 0 scale is straight up.10 wide one end edge of PET base material is located at 0 graduation mark
Place, is compressed with finger.The other end is naturally drooped along 3 graduation marks.Whether observation base material is close to graduation mark, if being close to quarter
Degree line then reaches flexibility requirements of the present invention.
The hardened layer of cure process layer 11 is mainly using radiation-curable coating, and coating is by polyurethane acroleic acid prepolymer tree
Fat, acrylic monomers, photoinitiator, required auxiliary agent and in order to reduce dope viscosity and adapt to thin-layer coating add in esters,
Ketone or benzene kind solvent composition.Using intaglio plate coating, film layer does 1~5u of thickness for coating, and ultraviolet light cures.
Cure process layer 11 is radiation-curable coating, and the raw material composition and parts by weight of the radiation-curable coating are：
Polyurethane acroleic acid prepolymer resin is using Shanghai Ke Li printing materials Co., Ltd；
Acrylic monomers is：Acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate a kind of extremely combination (on
Hai Kaiyin Chemical Co., Ltd.s)；
Photoinitiator is：Thioxanthones (triaryl salt compounded of iodine, triaryl salt) is used in mixed way photoinitiator；
Auxiliary agent is：Cellulose nitrate film forming agent, ethyl cellulose；
Solvent is：One kind of esters, ketone or benzene kind solvent and combinations thereof.
Further, in wherein some embodiments, radiation-curable coating also can be used directly：Middle painting chemical industry (Shanghai) has
Limit company UV glue, model EX-3215；Acrylic macromolecule resin Co., Ltd., Factory of Shantou City UV glue, model uv-124-3f.
Emphasis of the present invention is the silica gel flexibility and viscosity by controlling coating silica gel layer 12, improve non-deformability so as to
Achieve the effect that when protective film is bonded curved edge screen side will not be played.
Excellent flexibility possessed by organosiloxane comes from its basic geometrical molecular configuration, and the main chain of polysiloxanes is
A kind of spiral shape linear chain structure easily distorted is alternately made of silicon atom and oxygen atom, around the energy needed for the rotation of Si-O keys
Almost nil, this shows that the rotation of Si-O is free, this so that main chain is very submissive.Due to the rotation of methyl, these hydrogen are former
Son will occupy larger space, so as to add the distance of adjacent molecule, so the force ratio between polysiloxane molecule is hydrocarbon
Compound much weaker, thus obtained silicone oil is lower than the hydrocarbon viscosity of same molecular weight, and surface tension is small, film forming
By force.
Coating silica gel layer 12 uses organosiloxane synthetic paint.
The raw material of organosiloxane synthetic paint of the present invention forms and parts by weight are：
| Parts by weight | Raw material |
| 30~50 | Hydroxyl polysiloxane |
| 5~7 | Epoxy resin |
| 0.5~1 | Coupling agent |
| 0.005~0.01 | Curing agent |
| 0.01~0.05 | Catalyst |
| 45~70 | Solvent |
Wherein hydroxyl polysiloxane is as main chain；
Epoxy resin is referred to containing two or more epoxy groups, organic with fatty, alicyclic or aromatic series etc.
Object can simultaneously react the high-molecular oligomers for the crosslinkable thermoset products to be formed for skeleton by epoxide group, be changed with epoxy resin
Property organosilicon formed space network；It is introduced in soft segment in epoxy, advantage has：
1. adhesive properties are good, it is high to assign epoxy curing compound for active very big polar group in epoxy resin solidifying system
Adhesive strength, along with it has the mechanical properties such as very high cohesive strength, therefore its adhesive strength is especially strong, improve glue
Adhesion strength；
2. cure shrinkages are small, performance is stablized in solidification process, and levelability is good.
Coupling agent：Since polysiloxanes its molecular weight is excessive and the activity of end function base is caused to be restricted, the reaction because
This needs to react in high temperature environments；But self condensation reaction rate that high temperature results in silicones is too fast, flexibility link is very
The phenomenon that difficult all to participate in reaction, and this is susceptible to layering, selects positive silicic acid second cruel, poly- phthalein amine according to reaction speed；
Curing agent selects silica gel to prepare common dibutyl tin laurate, m-phenylene diamine (MPD)；
Catalyst：Good cross-linking reaction, so as to be the catalysis of all kinds of additional organosilicon reactions by painting platinum catalyst
Agent, it has the add-on type reaction being suitable for；
Hydroxyl polysiloxane has：Trimethyl triethoxysilane, diethylamino phenyl oxosilane, three ethoxy silane of aminomethyl phenyl；
Epoxy resin has：Phenol type novolac epoxy resin, o-cresol type novolac epoxy resin；
Coupling agent is selected：Positive silicic acid second is cruel, poly- phthalein amine；
Curing agent：Dibutyl tin laurate, m-phenylene diamine (MPD)；
Catalyst：Platinum curing agent (Shanghai SHIN-ETSU HANTOTAI organosilicon CAT-PL)；
Solvent：Toluene, dimethylbenzene, one kind and combinations thereof of ethyl acetate.
Embodiment：
As shown in Figure 1, testing standard according to the present invention, selects thickness as the higher PET base materials 10 of 38 μm of flexibilities,
PET base material 10 obtains cure process layer 11 in doing on one side at hardening, the hardening face thickness of cure process layer 11 is 3~4 μm；
The cure process layer 11 (hardened face) and attached last layer PET cuticular layers 20；10 another side of PET base material does silica gel treatment
Obtain coating silica gel layer 12,20 μm of 12 thickness of coating silica gel layer, attached last layer PET stripping films 30.
It, can also be (hard with cure process layer 11 again after PET cuticular layers 20 do silica gel treatment in wherein some embodiments
The inside at change) fitting；For example, PET cuticular layers 20, which are done, obtains silica gel treatment layer 21 after silica gel treatment, silica gel treatment layer 21 is separate
The one side of PET cuticular layers 20 is bonded with cure process layer 11.
The silica gel treatment method：There are the hydroxyl polysiloxane (linear polysiloxanes) that will centainly match, coupling agent and molten
Agent adds in agitating and heating 4~6h of reflux (hour), then adds with epoxy resin high-volume, return stirring 2h (hour), with
It is steamed afterwards by solvent under reduced pressure to solid content 80% or so, then is warming up to 80~100 DEG C, add in coupling agent, back flow reaction 2h is (small
When), you can obtain organic siliconresin.5h (hour) is stood, adds in curing agent and catalyst stirring 1h (hour).
Embodiment described above only expresses some embodiments of the present invention, and description is more specific and detailed, but simultaneously
Cannot limitation of the scope of the invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection model of the present invention
It encloses.Therefore, protection scope of the present invention should be determined by the appended claims.
Claims (3)
1. a kind of protective film for being bonded arc side, includes：PET base material (10), which is characterized in that PET base material (10) is done on one side
Cure process obtains cure process layer (11), and PET base material (10) another side does coating silica gel and handles to obtain coating silica gel layer (12),
One side attached last layer PET stripping film (30) of the coating silica gel layer (12) away from PET base material (10), cure process layer (11) are separate
The attached last layer PET cuticular layers (20) of one side of PET base material (10)；
PET cuticular layers (20) do and obtain silica gel treatment layer (21) after silica gel treatment, and silica gel treatment layer (21) is away from PET cuticular layers
(20) one side is bonded with cure process layer (11)；
The hardened layer of cure process layer (11) mainly using radiation-curable coating, the raw material composition of the radiation-curable coating and
Parts by weight are：
Acrylic monomers is：Acrylic acid, methyl acrylate, ethyl acrylate, one kind and combinations thereof of butyl acrylate；
Photoinitiator is：Thioxanthones is used in mixed way photoinitiator；
Auxiliary agent is：Cellulose nitrate film forming agent, ethyl cellulose；
Solvent is：One kind of esters, ketone or benzene kind solvent and combinations thereof；
Coating silica gel layer (12), silica gel treatment layer (21) use organosiloxane synthetic paint, organosiloxane synthetic paint
Raw material forms and parts by weight are：
Trimethyl triethoxysilane, diethylamino phenyl oxosilane, three ethoxy silane of aminomethyl phenyl one kind and its
Epoxy resin is selected：Phenol type novolac epoxy resin, one kind of o-cresol type novolac epoxy resin and combinations thereof；
Curing agent is selected：M-phenylene diamine (MPD)；
Catalyst：Platinum curing agent；
Solvent：Toluene, dimethylbenzene, one kind and combinations thereof of ethyl acetate.
2. a kind of manufacturing method for the protective film that can be bonded arc side as described in claim 1, which is characterized in that manufacturing method is such as
Under：
(1), thickness is selected as the higher PET base material (10) of 20~50 μm of flexibilities, in PET base material (10) is done at hardening on one side
After obtain cure process layer (11), the hardened layer of cure process layer (11) hardens face thickness mainly using radiation-curable coating
For 3~4 μm, using intaglio plate coating, film layer does 1~5 μm thick, ultraviolet light curing for coating；
(2), the attached last layer PET cuticular layers (20) outside cure process layer (11)；
(3), do the high silica gel treatment of flexibility in PET base material (10) another side and obtain coating silica gel layer (12), 20 μm of thickness；
Silica gel preparation method：Proportioned trimethyl triethoxysilane and solvent are added in into 4~6h of agitating and heating reflux；Then
Add the epoxy resin of formula ratio, return stirring 2h；Then solvent under reduced pressure is steamed to solid content 74~86% again, then is heated up
To 80~100 DEG C, polyamide, back flow reaction 2h are added in, you can obtain organic siliconresin, stand 5h, add in curing agent and catalysis
1h is stirred in agent；
(4), attached last layer PET stripping films (30) outside coating silica gel layer (12).
3. manufacturing method according to claim 2, which is characterized in that in step (2), PET cuticular layers (20) internal layer does silicon
Silica gel treatment layer (21) is obtained after glue processing, silica gel treatment layer (21) is bonded again with cure process layer (11).
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| CN201510447066.XA CN105176370B (en) | 2015-07-27 | 2015-07-27 | A kind of protective film and its manufacturing method for being bonded arc side |
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|---|---|---|---|
| CN201510447066.XA CN105176370B (en) | 2015-07-27 | 2015-07-27 | A kind of protective film and its manufacturing method for being bonded arc side |
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| CN105176370A CN105176370A (en) | 2015-12-23 |
| CN105176370B true CN105176370B (en) | 2018-05-22 |
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| CN105522799A (en) * | 2016-01-13 | 2016-04-27 | 东莞市纳利光学材料有限公司 | Hot-press molded protective film with shinning and antistatic effects and preparation method thereof |
| CN106079775B (en) * | 2016-06-29 | 2018-06-01 | 东莞市纳利光学材料有限公司 | A kind of protective film with unlocked by fingerprint and preparation method thereof |
| CN107187128B (en) * | 2017-04-29 | 2019-04-02 | 广州易航电子有限公司 | A kind of curved surface protective film and its laminating method of coating and forming method |
| US20210185158A1 (en) * | 2018-08-31 | 2021-06-17 | Huawei Technologies Co., Ltd. | Flexible protective film, curved display, and terminal |
| CN109943250B (en) * | 2019-03-29 | 2021-06-25 | 浙江欧仁新材料有限公司 | Glue residue prevention silica gel protective film for manufacturing process |
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| JP2014125567A (en) * | 2012-12-26 | 2014-07-07 | Nippon Denshi Seiki Kk | Re-peelable type self-tack film |
| CN103614089B (en) * | 2013-11-22 | 2015-07-15 | 东莞市纳利光学材料有限公司 | Golden blue ray-resistant protection film and preparation method thereof |
| CN104592908B (en) * | 2014-12-26 | 2016-08-17 | 东莞市纳利光学材料有限公司 | A kind of preparation method and application of the protecting film of mobile terminal of can comprehensively fitting |
| CN104789075B (en) * | 2015-04-15 | 2017-02-22 | 苏州创佳电子材料有限公司 | Hard information coating for screen protective film as well as preparation method and application of hard information coating |
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